Binary emulsifiers



United States Patent r a BINARY: EMULSIFIERS IblinT..Patton,tlr.;wyandotte, Micln, assiguor toLWyani dotteClr'emicals'corporation, Wyandotte, Michz, acor Noam-Me a Filed Ma fl31,=19s7-,senNmsaasss.

8Claims. (Cl. zen-sear I This application is. a co'ntinuat'iomin-part of U.S.' patent application', Seria1 No. 466,954, filed November 4, 1954,, for Surface Active Agentsfi now abandonedl "The presentinventionrelates to binary emulsifiers conjsisting essentially of higher aliphatic acid and rosin acid esters of certain totally hydroxyalkylated alkylene polyamines, and theoxyethylated adducts of these same higher aliphatic; acid esters;

The"compounds-ofthezpresent invention are derivatives "oficertain totally"hydroxyalkylatedalkylene polyamines. Theqiirsf class of totally hydroxyalkylatedalkylenepoly: amines used" as intermediates: in preparing the compounds off the: present invention arej thetotallyhydiioxypropylated and the totally" hydroxyhutylated alkylene diamines' conforming to the formula: t

l "RLW Rio wherein R is an alkylene group-cont aining 2 to.6 carbon Eatented July. 5, 1-9 6);

yl-;2-hydroxypropy1 group. A typical pound conforming tothe above formula is i 'N,N, N',N",N-". i V pentakis(2-hydroxypropyl)diethylene triarnine. 'The to, tally hydrox-yalkylated alkylene polyamines used in. the

synthesis. of the compoundsoffthe presentlinvention are a readily prepared: by condensing propylene oxide, 1,2 butylneoxide or 2,3 -butylene oxide or'mi'xtures thereof with "an appropriate alkylene polyamine in the pres= enceLotL water at'a temperature of 40-120 C. The

' quantity of oxide .usedin the condensationreaction is atoms, and R R3;-.'and R areselected; from. :the groupreonsisting? ofrthe 2-hydroxypropylr group, the 2- 1 :la-ydroxyllautyl? group and! the 1,-methyl-2ehydroxypropyl arcane-lem i ete al r hy r xy l da y 'di-aminesconforming to the above formula is N,II,'l I",lI

tetrakis(Z-hydroxypropyl) ethylene diamine. The second t class ofto ally ,hydroxyalkylated alkylene poly-amines used as ediatesifi preparing the compounds "of'tlie present? iilv on! are, the totally hydroxypropylated and flie tbflll'i" hydroxynutylat'ed' 1",3'-diamino 2 propano1s conforming fo'the f ormula-z H no on; t. 11a;

sienna? RE" RI wherein R R R and R are selected from the group cane-sting of mag 2 hydroxyp'ropy1 group, the 2%hydroxy- 'bnt yl group and the I-methyl-Z-hydroxypropylgroup. A

"typica1 exa m 1e of: the compounds conforming to the alioveformula is N",N",N",N{ tetrakis (2 hydroxypropyljl idiafiiino-z-propanol. The third class of totally hydroxyalkylated' alkylene polyamines used as intermediates "iirpreparing the compounds-of the present invention are the; may hydrox'ypropylatecl and the; totallyghydroxyme conforming to the formulas wherein R is an alkylene radical selected from the group consisting of ethylene and' propylene radicals, n is an se .-n h w -awereBant m selected fiom the-groupconsistingofi th a, t, v. ,WH i S f: piopyl group, the 2-liyd'roxybuty1 group and the l-methprorated polymers of ethylene diamine' andpr opylene dij- J suchwas to furnish, one mol of oxide for each. a-mino'hydrogen; of the polyamine.

Thehigherefatty acid and. rosin acid. esters of the to.- tally hycl'roxyall'q'latedw alkylene polyaminesof the pres-' ent invention are prepared by esterifying the totally hyadroxyalkylated: 'alkylene. polyamine of interest with a fatty acid or rosin acid containing at. least 8 carbon atoms in-'its structure. Hereinafter, for convenience, the above compounds frequently will-be refer-red to simply as Fhigher esters. Typicalofithe-higher esters coming within the scope oftherpresent invention is the monostearate. ester of tetrakis(2 hydroxypropyl)ethylene diamine which has thefollowing chemical structure:

7 o on, on, onr(oHr)m-i io-en-on,- 0H,.- n-on lN -cH-rCflr-N' He -e396 '2 CHPGHOBF The higher estersmay be prepared by conventional esteriiicationte :l1'i11'que' s as for example by simply heating a higher fatty acid' and a totally hydroxyalkylated alkyl ene polya-r'nine; 1 v

or this-invent Typical examples of such acids are Z-etliylhic'andie acid; octanoic acid, undeca'noicacid, lauric acid, myristic acid, pahniticacid; abie'ticacid; etc. When an aliphatic acid is used in preparing the compounds of interest, it? is" preferred fto employ acids having a low degree of unsaturation such as stearic and oleic acids except Where the ester is to be used as an intermediate inthe preparation of surface coating compositions. It is not necessary to use single acids in. preparing. the desired? higher; esters as products with desirable ylene diamine'andr perhaps minorrtraces of, the triand tetrastearate esters. {For convenience iii-description in the subsequent discussionof the invention the esterification productswilllbereferred to simply as the mono-,fldi, .tri'ror tetraesters,,rsine such desi gnation identifies the principal constituent oftheprodil'ct. Although. individual esters can be isolafedhy complicated proceduressuch 'as example of. a'con 1-j Essentially any 8for higher 'about 20 being about the praeticaFjupperf "init only because ofwhat' is available in comni'erei'aI qtiantities) carbonatomiialiphatic acid or rosinacid may be used in preparin'gfth'e" compounds repeated 'molecular distillations, such purification is not required since the esterification products asproduced have excellent surface active properties.

The higher esters of the totally hydroxyalkylated allgyl: ene polyamines are lipophilic surfac e active agents having low HLB numbers as determined by the method of W. C.- Grifiin, Journal of the Society ofjC -osmetic Chemists, 1, 419 (December .1949). The higher esters per se have utility as surface active agents in many non-aqueous systems and are also employed in conjunction with their oxyethylated derivatives to form multicomponent emulsifier systems. The simple acid salts of the higher esters, e.g. the hydrochloride and acetic acid salts, are water-soluble and are excellent emulsifiers. These latter emulsifying agents are extremely useful, since emulsions prepared therewith can be easily resolved by simply adding a small quantity of base to the emulsion. The higher esters, particularly the tetraesters, derived from aliphatic acids containing high degrees of unsaturation, e.g. linoleic acid, function as drying oils and may be usedin surface coating compositions. The monoand diesters derived from the highly unsaturated aliphatic acids may be used as intermediates in preparing oil modified alkyd resins.

The oxyethylated adducts of the higher esters of the totally hydroxyalkylated alkylene polyamines are prepared by adding ethylene oxide to the higher esters in the presence of an alkaline catalyst. The solubility characteristics of the oxyethylated adducts depend primarily on the percent oxyethylene content of the adduct and vary from lipophilic essentially water-insoluble products when the oxyethylene content is small to completely water-soluble products such as are obtained when the adduct contains 50% of oxyethyleneg roups. The oxyethylene adducts of low oxyethylene content, e.g. 525% somewhat resemble the higher esters themselves in properties and are in the main excellent emulsifiers. The properties change gradually and the products become increasingly more water-soluble as the oxyethylene content of the derivatives is increased. The water-soluble higher oxyethylated esters, e.g. those containing 25-75% of oxyethylene groups, are excellent laundry detergents and have a high loading power for removing oily soils from textiles. Many interesting emulsifying systems can be prepared by combining both a higher .ester and an oxyethylated adduct of a higher ester to form binary and even more complex emulsifiers.

, The following examples are set forth to more clearly illustrate the principle and practice'of the invention to those skilled in the art.

EXAMPLE 1 Part A A total of 216 grams (1.5 mol) of 2-ethylhexanoic acid, 292 grams (1 mol) of N,N,N',N tetrakis(2-hy- Part B The di-2-ethylhexanote ester of N,N,N',N' tetrakis(2- hydroxypropyDethylene diamine is prepared as described in Part A above except that initially 2.5 mols of 2-ethylhexanoic acid is charged to the reaction and the esterification is continued until 36 ml. of water is collected which indicates the formation of the diester.

XAMPLE Part A Stearic acid and N,N,N',N tetrakis(2-hydroxypropyl) ethylene diamine are charged in an equal molar ratio to the apparatus described in Example 1, Part A, that is modified in that the decanting head is replaced with an ordinary distillation takeofi head. The reaction mixture is heated for approximately 4 hours atreflux temperature and atmospheric pressure and then under vacuum at 160.? C. until the reaction is complete. Heating is continued until titration of the reaction mixture indicates that all of the stearic acid has been esterified. The product is the monostearate ester of N,N,N',N' tetrakis(2-hyd'roxypropyl)ethylene diamine.

Part B I The distearate ester of N,N,N',N'- tetrakis(2-hydroxypropyl)ethylene diamine is prepared as described in. Part A above except that 2 mols of stearic acid are charged for each mol of the N,N,N',N tetrakis(2-hydroxypropyl) ethylene diamine.

Part C The monostearate esters of N,N,N',N' tetrakis(2-hy.- droxypropyl)-1,3-diamino-2-propanol, N,N,N',N tetrakis- (2-hydroxybutyl)ethylene diamine and. N,N,N,N",N' N' hexakis(2-hydroxypropyl)triethylene tetraamine are prepared as in Part A except for the substitution of the totally hydroxyalkylated alkylene diamine of interest for the N,N,N',N' tetrakis(2-hydroxypropyl)ethylene diamine of Part A. g

The triand tetra-fatty acid esters can be prepared by the techniques of Examples 1 and'Z by simply increasing the mol ratio of fatty acid to totally hydroxyalkylated alkylene polyamine.

' EXAMPLES 3-8 Additional esters of N,N,N',N tetrakis(2 -hydroxypropyl)ethylene diamine are prepared by esterification with lauric acid, oleic acid and tall oil (a mixture of fatty TABLE I Example No. Ester Prepared- 'Monooleate.

Dloleate. Monolaurate. Dilaurate.

Mono tall 011 ester. 1)! tall 011 ester.

.The specific esters set forth in the above examples are merely illustrative of the invention and analogous products can be prepared by esterifying fatty acids and/or rosin acids containing at least 8 carbon atoms with other totally hydroxyalkylated alkylene polyamines such as N,N,N',N tetrakis l-methyl-Z-hydroxypropyl) 1,3-diamino-2-propanol, N,N,N',N' tetrakis(2-hydroxybutyl)1,3-diamino-Z-propanol, N,N,N',N' tetrakis(2'-hydroxypropyl) hexamethylene diamine, N,N,N',N' tetrakis(2-hydroxybutyl) propylene diamine, N,N,N',N' tetrakis(l-methyl-2- hydroxypropyDethylene diamine, N,N,N',N,N" pentakis(2-hydroxypropyl)diethylene triamine and N,N,N',N", N'", N hexakis(Z-hydroxybutyl)-triethylene tetraamine.

EXAMPLE 9 Part A N tetrakis(2-hydroxypropyl)ethylene diamine"of Exbinary mixtures of emulsifiers ample 3 9 piiitjbfiflirbI-Tcatalyst are charged intbia stainl'ess steelautoclaveequipped with Il arca to ishqat dr e 25e and 9 par tsqfliy s i ox de are. dd dte-the e -mi tl e t t- 9 mem y ns adduc pi y e erscataimns z t ae rq y e groups upr s n s .it. wi

Part B Part A is repeated except that the amount of'ethylene oxide addedis sufiicient to prepare an oxyethylene adduct containing 33% of oxyethylene groups.

Part C Part A is repeated except that the amount of ethylene A oxide added is sufiicient to prepare an oxyethylene adduct containing 67% of oxyethylene groups.

EXAMPLES 10-28 Oxyethylene adducts of the fatty acid esters of N,N,N', N tetrakis(2-hydroxypropyl)ethylene diamine prepared in Examples 1, 2 and 4-8, inclusive, are prepared by adding varied quantities of ethylene oxide to the fatty acid esters following the procedure of Example 9. The composition of the products produced is set forth in Table H.

TABLE II v Oxyethylene Gon- Example N0. Intermediate Ester tent of a Product,

' percent W 10 M'nn nlnn'ratn 50 11 do 60 12 67 13.- Dllaurate 67 14 rln 75 15 Dinlnato 67 o. 75 17 Mm-m tomato 5O 1R do 60 m rln 7 an Distonrat 57 21 n 75 22 Mono tall oil ester 23 do 33 24 do 50 25 6D 26 67 27 Di tall oil ester 67 28 do 75 EXAMPLE 29 Stable emulsions of xylene in water are prepared .employing several binary mixtures of emulsifiers. The comprise in each case a fatty acid ester of N,N,N',N tetrakis( 2-hydroxypropyl) ethylene diamine and an ethylene oxide adduct of the same fatty acid ester. The procedure is to add 2.4 grams of the binary emulsifier which is composed of 0.6 gram of the fatty acid ester and 1.8 grams of the ethylene oxide adduct of the fatty acid ester, 9.6 grams of xylene in an 8 ounce wide mouthed bottle and then stir vigorously withan electric stirrer while continuously adding 48ml. of water dropwise over a period of 15-20 minthis-example are set forth in Table III.

"T BL T I .7

" Oomposition'Mixed Emulslfien 1 Mlxed Emulslfleii :Hi'gher Fatty. Oxyethylated: I

Ester, Product A du a of Example Producto'fj No.- Example No.-

A l 9, Part C. B 9, Part D.

0.- 4 15. D 5 10. E- 2, Part A 18. F 2, Part A 19. G 2, PartB 20. H 2, Part B 21. T a 13. J 6 14.

What 1s claimed 1s:

1. A binary emulsifier consisting of about 25 weight percent of (a) an amino-ester having the formula wherein R R R and R are monovalent radicals selected fiom the group consisting of radicals having the formulae CH CH(OH) CH --CH CH(OOCR CH -CH CH(OH)CH CH --CI-I CH(QOCR )CH CH -CH(CH )CH(OH)CH and wherein in said radical formulae R is selected from-the group consisting of aliphatic hydrocarbon radicals having from 8 to 20 carbon atoms and abietyl radical, at least 1 and not more than 2 of said R R R and R radicals containing an R radical in its structure; and

wherein R is 'a divalent radical selected from the group 'consistingof alkylene radicals having 2 to 6 carbon atoms, 2-hydroxy-1,3-propylene, and radicals represented by the formula [---R N(R wherein n is an integer not higher than 2, R is a divalent radical selected from the group consisting of ethylene and propylene and R is a monovalent radical as hereinbefore defined and (b) about 75 weight percent of the corresponding adduct of (a) with from about 50 to about 75 weight percent of ethylene oxide.

2. A binary emulsifier according to claim 1 wherein in the amino ester R is ethylene, 3 of R R R and R are CH CH(OH)OH and l of R R ,R and R is -CH CH(OOCR )OH and R is an aliphatic hydrocarbon radical having 8 to 20 carbon atoms.

3. A binary emulsifier according to claim 1 wherein in the amino ester R is ethylene, 2 of R R R and R are --CH CH(OH) CH and 2 of R R R and R are CH CH(OOCR )CH and R is an aliphatic hydrocarbon radical having from 8 to 20' carbon atoms.

4. A binary emulsifier according to claim 2 wherein inthe amino ester OOCR represents an oleate radical and the adduct (b) contains 60 weight percent of ethylene oxide.

5. A binary emulsifier according to claim 2 wherein OOCR represents an oleate radical and the adduct (b) contains 67 weight percent of ethylene oxide.

6. A binary emulsifier according to claim 2 wherein in the amino ester -OOCR represents a stearate radical and the adduct (b) contains 60 weight percent of ethylene oxide.

7 7. A binary emulsifier according to claim 3 wherein V V References Cited inthe file of this patent OOCR represents atstear'ate radical and the adduct 7 7 (b) contains75 weight percent of ethylene oxide. f T 'PA E Q 8. 'A binary emulsifier according to claim 2 wherein 2; 248,729' Ulrich'etal. July 8 '1941 in'the amino ester OOCR represents a laurate radical 5 2,262,738 De'Groote and the adduct (b) contains 50 weight percent of ethylene 2366,498 IDe'G'r'dote et a1 oxide. Y 2,382,61'2' DeGi'ote et 'ali 

1. A BINARY EMULSIFIER CONCISTING OF ABOUT 25 WEIGHT PERCENT OF (A) AN AMINO-ESTER HAVING THE FORMULA 